Pesticidal 1-amino-1-mercapto-2-cyano-ethene derivatives

ABSTRACT

Pesticidal, e.g. herbicidal, fungicidal and/or defoliating, compounds are provided of the following formula: WHEREIN R1 represents CN; CONH2; CONHCH3; or COOR2, R2 and R3 each represents hydrogen or alkyl of one to five carbon atoms, or together with the common N-atom, a piperidino, pyrrolidino or morpholine ring, and R4 is hydrogen, NH4 , an equivalent of a metal cation, or

limited States Patent Joos PESTICIDAL l-AMINO- l-MERCAPTO-Z-CYANO-ETHENE DERIVATIVES Alfred J'oos, Frankfurter strasse 250, 61Darmstadt, Germany Filed: June 17, 1969 Appl. No.: 834,176

Inventor:

Foreign Application Priority Data June 24, 1968 Germany ..P 17 68 784.2

11.5. CI. ..260/465.4, 71/88, 71/94, 71/95, 71/97, 71/98, 260/2471,260/293.85, 260/326.84, 260/429.9, 260/430, 260/431, 260/438.1, 260/439,260/465.5 R

lnt. Cl ..C07c 121/30 Field of Search ..260/465.4, 465.5, 469.8, 464

References Cited UNITED STATES PATENTS Edwards ..260/465.4 XDickinson.... ..260/465.5 X

Vest ..260/464 Laliberte ..260/465 X Laliberte ..260/465 .4 X Laliberteet a1. ..260/465 .4 X

Primary Examiner-Joseph P. Brust Attorney-J. William Millen Mar. 27,1973 ABSTRACT Pesticidal, e.g. herbicidal, fungicidal and/ordefoliating, compounds are provided of the following formula:

22 Claims, No Drawings PESTICIDAL l-AMINO-l-MERCAPTO-2-CYANO- ETIIENEDERIVATIVES wherein R represents CN; CONH CONI-ICH or COOR R and R eachrepresents hydrogen or alkyl of one to five carbon atoms, or togetherwith the common N-atom, a piperidino, pyrrolidino or morpholino ring,and

R,, is hydrogen, NHf, an equivalent of a metal cation, or

To produce these compounds, an ethene compound of Formula II N C R5 R3II wherein R, to R have the previously indicated meanings, and Rrepresents halogen or alkylthio of one to four carbon atoms, is reactedwith alkali metal, alkaline earth metal or ammonium sulfides orhydrosulfides in an inert solvent at temperatures of between -20C and+l00C. A thusobtained mercaptan derivative can then be converted into amercaptide of Formula I; or alternatively, a thusproduced mercaptide canbe converted into the corresponding mercaptan by treatment with an acid.Both compounds can be converted into a disulfide of Formula I bytreatment with an oxidizing agent.

In all compounds of formulas I and II, the substituent -NR R can be inthe cisor trans-position with respect to R The compounds of Formula Iare active pesticidal agents especially in plant treatment, preferablyas fungicides, herbicides or defoliants. In particular,bis-(lmethylamino-Z-cyano-2-aminocarbonyl-ethenyl)- disulfide shows agood herbicidal activity. Furthermore, nematocidal effects occur, f.e.in bis-(l-amino- 2,2-dicyan0-ethenyl)-disulfide.

The disulfides in particular of Formula I are usable as vulcanizationaccelerators when used in conventional amounts. The compounds of FormulaI are also valuable intermediates for the preparation of other effectiveagents for pest control, or for plant treatment, particularly for theproduction of effective agents on the basis of thiocarboxylic acidamides and isothiazole derivatives. For instance, treatment ofmercaptides of Formula I (R, equivalent of a metal cation, preferablyNa) with chlorine gives 3-chloro-4-R,-5-NR R -isothiazoles such as3-chloro-5-amino-4-isothiazolecarbonitrile or3-chloro-5-amino-4-isothiazolecarboxamide which are described in US.Pat. No. 3,155,678 being useful as herbicides or intermediates for themanufacture of dyes and which can be used, furthermore, as intermediatesfor the manufacture of valuable insecticides and/or herbicides asdescribed in copending application Ser. No. 628,569.

Referring now to the various R groups of Formula I, R in addition to theresidues CN, CONHCI-I and CONH includes the residues COOR wherein R islower alkyl of up to five carbon atoms, e.g. CH C H nC H i-C I-I-,, n-CI-I iC I-I tert.C H ,n amyl or isoamyl, with methyl and ethyl beingespecially preferred. R and R can, in each case, be either identical ordifferent but, of course, do not simultaneously represent groups whichcannot form part of the same molecule because of steric hindrance, e.g.R and R do not simultaneously represent tert.C l-l With respect to novelcompounds per se, R represents COOR only when the compound of Formula Iis a disulfide.

Among the mercaptides of Formula I (R, equivalent of a metal cation orNI-If), especially im portant are the sodium, potassium, silver, zinc,mercury, iron and copper mercaptides.

Several of the preferred ethene compounds include, but are not limitedto: l-amino-l-mercapto-2,2- dicyano-ethene; l-methylaminol-mercaPto-2,2- dicyano-ethene; l-dimethylaminol -mercapto-2,2-dicyano-ethene; l-piperidino-l-mercapto-2,2-dicyanoethene;l-pyrrolidino-l-mercapto-2,2-dicyano-ethene;l-morpholino-l-mercapto-2,Z-dicyano-ethene;l-mercapto-l-amino-2-cyano-2-aminocarbonyl-ethene;lmethylamino-I-mercapto-2-cyano-2-aminocarbonylethene;l-dimethylamino-1-mercapto-2-cyano-2- methyl-aminocarbonylethene;l-amino-l-mercapto-Z- cyano-2-carbethoxy-ethene; l-methylamino-l-mercapto-2-cyano-2-carbethoxy-ethene;l-dimethylamino-lmercapto-2-cyano-2-carbethoxy-ethene; andlisopropylamino-1-mercapto-2-cyano-2-carbomethoxyethene. Of additionalimportance are the salts of these compounds, in particular the sodium,potassium, am-

monium, silver, zinc, mercury, iron or copper mercaptides of thesecompounds.

Furthermore, the corresponding disulfides represent a preferred group,including, but not limited to, the following examples:bis-(l-amino-2,2-dicyano-ethenyl)- disulfide;bis-(l-methyl-amino-2,Z-dicyano-ethenyl)- disulfide;bis-(l-dimethylamino-2,Z-dicyano-ethenyl)- LllSUlfldC', bis(l-pipcridino-2,Z-dicyanoethenyl)-disulfide; bis-( l-pyrrolidino-2,Z-dicyano-ethenyl)-disulfide;bis-(l-morpholino-,Z-dicyano-ethenyl)-disulfide; bis-(l-amin-2-cyano2-aminocarbonyl-ethenyl)-disulfide; bis-( 1-methylamino-Z-cyano-Z-aminocarbonyl-ethenyl)-disulfide; bis-(l-dimethylamino-2-cyano-2- aminocarbonyl-ethenyl)-disulfide; bis-( 1dimethylamino-2-cyano-2-methylaminocarbonyl-ethenyl)-disulfide; bis-(l-amino-2-cyano-2-carbethoxyethenyl)-disulfide;bis-(l-methylamino-2-cyano-2-carbethoxy-ethenyl)-disulfide;bis-(l-dimethylamino-2- cyano-2-carbethoxy-ethenyl)-disulfide; andbis-(1- isopropylamino-2-cyano-2-carbomethoxy-ethenyl)- disulfide.

The substituent R in the starting materials of Formula II can be, inaddition to halogen, lower alkylthio of up to four carbon atoms (-SCH SCI-I S nC H,, -SiC H,, SnC I-I Si-C,,H or Stert.C,I-I,,), wherein theresidue SCl-I is preferred. Among the halogen residues, Cl, Br and I arepreferred.

It was surprising that the reaction of the compounds of Formula II withthe sulfides or hydrosulfides takes place so smoothly and with suchextraordinarily high yields. Such a reaction has not been knownheretofore. It was actually expected that, under the reaction conditionsemployed, wherein perforce a very strongly basic reaction medium isproduced, the CN-group(s) would be saponified. However, in actuality, nohydrolysis takes place; rather the mercaptans or mercaptides of FormulaI are surprisingly obtained in an almost quantitative yield. Moreover,when starting with compounds II containing the residue R loweralkylthio, the process proceeds by way of a previously unknown thioethersplitting step. That this thioether splitting reaction is conducted sosmoothly is also surprising and has not been described heretofore in theliterature.

When conducting the process, the starting materials II are suitablysuspended or dissolved in an appropriate medium. For example, thestarting compounds can be suspended in water, optionally with theaddition of an organic solvent. Especially suitable organic solvents, inthis connection are: lower alcohols, such as methanol, ethanol,isobutanol or polyhydric alcohols, especially lower dior triols, such asglycol or glycerin, water-miscible ethers, such as tetrahydrofuran ordioxane, or dimethyl formamide.

In addition to the ammonium compounds, suitable alkali sulfides orhydrogen sulfides are, in particular, the Naand K-compounds, while thepreferred alkaline earth salts are the Caand Mg-sulfides or hydrogensulfides.

The suspension or solution of the starting compounds is then combinedwith the sulfide or hydrosulfide. The sulfide or hydrosulfide issuitably employed in a molar ratio of l l to 2 1, based on the startingcompound. In general, the sulfide or hydrogen sulfide is utilized in theform ofa solution, for example, in a 1-50 percent, especially aqueous,solution. For instance, a commercially available 33 percent sulfidesolution can be employed. The reaction is generally terminated after afew minutes to about 10 hours at a temperature of between about 20C and+IOOC, preferably at about +20C to +C, the reaction being acceleratableby agitation of the mixture. The reaction mixture is worked up in theusual manner.

If the starting compound is one of Formula II containing the residue Rhalogen (preferably Cl, Br or I), a mercaptan is obtained by reactingwith a hydrosulfide. When reacting with sulfides, correspondingmercaptides are obtained. Likewise, starting materials of Formula [Iwherein R lower alkylthio yield mercaptides of Formula I.

If desired, the thus-obtained mercaptides can be converted into the freemercaptans of Formula I by adding an acid. Suitable acids are primarily:mineral acids, such as hydrochloric acid, hydrobromic acid, sulfuricacid, perchloric acid or phosphoric acid; or also organic acids,especially lower carboxylic acids, such as oxalic acid, formic acid,acetic acid, propionic acid or butyric acid. In place of an acid, it isalso possible to employ acid salts, for example, acid sulfates, acidphosphates, acid oxalates or acid tartrates. Preferred are the strongmineral acids. The mercaptides can be subjected to the mineral acid byemploying the latter, for example, in an approximately 10 percentsolution.

A thus-obtained mercaptan I can, if desired, also be converted into amercaptide in a conventional manner. Also, a mercaptide I can beconverted into another mercaptide I. In this connection, for example,the preparation of heavy metal mercaptides is of importance, forexample, copper, iron, silver, mercury or zinc mercaptides frommercaptans or other mercaptides of Formula I. Thus, it is possible toobtain heavy metal mercaptides, for example, in a simple manner bydissolving alkali or ammonium mercaptides of Formula I in a suitablesolvent, e.g., in alcohols, and adding thereto a heavy metal salt, e.g.,zinc acetate, which is likewise soluble in this solvent. The poorlysoluble heavy metal mercaptide is precipitated from the solution and canbe isolated in a simple manner, for example, by filtration.

In general, the readily soluble mercaptides, e.g., alkali or ammoniummercaptides, can be converted into the corresponding, poorly solubleheavy metal mercaptides I in a conventional manner, preferably byreaction with a corresponding heavy metal hydroxide suitable for thesalt formation, or with heavy metal salts of weak acids, for example,with acetates such as copper(l)- or silver acetate, or carbonates orcitrates, or with iron, zinc or mercury acetates, carbonates orcitrates. Another suitable example is ferroammonium sulfate. In place ofheavy metal salts of weak acids, it is also possible to employ the metalsalts of strong acids, together with a buffer salt. Thus, for example,copper mercaptides of Formula I can be produced from the correspondingmercaptans or readily soluble mercaptides I by reaction with coppersulfate in the presence of sodium acetate. Correspondingly, I-IgCl canbe used in the presence of sodium acetate.

The mercaptans or mercaptides of Formula I can also be converted intothe corresponding disulfides by treatment with an oxidizing agent. Inthese disulfides, R represents For this oxidation reaction, alloxidizing agents can be employed which are conventionally employed forthe preparation of disulfides from mercaptans or mercaptides. Especiallysuitable for this reaction are the following oxidizing agents: air in analkaline or ammoniacal solution, optionally with the use of iron saltsor copper salts as catalysts; 11 in an acidic or ammoniacal solution,optionally together with iron salts as the catalyst; halogens,especially chlorine, bromine, or iodine, preferably in water or organicsolvents, such as glacial acetic acid or acetonitrile; alkalihypohalogenites, e.g., sodium hypochlorite; FeCl in an aqueous solution;1( Fe(CN) in an aqueous solution; nitric oxide in an alkaline solution;peracids, or the salts thereof, such as ammonium persulfate;permanganates; and nitric acid.

The starting materials 11 are, for the greater part, known or otherwisecan be prepared in accordance with conventional methods known from theliterature. Particularly relevant in this respect is South African Pat.No. 66/5910 and the literature cited therein.

When the mercapto compounds of Formula 1 are oxidized to disulfides, itis not necessary to isolate the former. Rather, the reaction solutionobtained, containing the mercaptan, can be directly subjected to theoxidation process.

The novel compounds of this invention can be employed as effectiveagents in combatting plant pests. They can be employed as fungicide inthe open fields, or also in seed-dressing agents. Furthermore, thecompounds are also effective as herbicides, in certain cases also asdefoliants, e.g., for defoliating cotton. In this connection, they canalso be combined, in a conventional manner, with other, known effectiveagents.

The ethene derivatives of the present invention can be processed intoall forms of application conventional for pest control or planttreatment. With the addition of the conventional carriers and/oradditives, it is possible, for example, to produce spraying or dustingcompositions, as well as dressing compositions for the preservation ofseed. These compositions usually contain further additives, such asdispersing and/or wetting agents. When appropriate additives areemployed, it is also possible to work the substances into solutions oremulsions which can, for example, also be sprayed as aerosols, with theusual propellant gases being employed. A preferred composition comprisesactive agent, surface active agent and pulverulent solids.

Emulsion concentrates can be made available commercially as such; beforeuse, the emulsion concentrates are diluted with water in the usualmanner. In case compositions are employed containing, as theeffective-agent components, one or more water-soluble substances, it is,of course, also feasible to employ water as the solvent or diluent forproducing the concentrate.

The total content of active agent in the compositions to be applied toplants ranges generally between 0.1 and 95 percent, preferably between20 and percent. In combination preparations, the proportion of theproducts of this process in the total proportion of effective agentnormally ranges between 0.1 and percent, preferably between 10 and 60percent.

The rate of application is in dependence on the effect desired, theclimatic conditions, and the type and character of the plants to betreated between 1 and kg/ha, preferably between 3 and 20 kg/ha [1hectare being 2.471 acres].

Compounds of Formula I in which R represents COOalkyl, R and R representalkyl or, together, alkylene, and R represents H are described in GermanPat. No. 1,237,105.

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention toits fullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative, and not limitative ofthe remainder of the disclosure in any way whatsoever.

I. PREPARATION OF THE COMPOUNDS EXAMPLE 1 139 g. 1 mol) ofl-amino-l-methylmercapto-2,2- dicyano-ethene is suspended in 4 l. ofwater. Then 169 g. of 33 percent sodium hydrogen sulfide solution isadded, and after the reaction solution is heated under agitation for 4hours to 80-85C, the solution is concentrated under reduced pressure at80C to about 1 liter, and then cooled to 20C. In case the solution doesnot remain clear, it is subjected to filtration, and the filtrate isevaporated to dryness at about 80C under a vacuum. As the residue, 136g. (92.5 percent of theory) ofl-amino-l-sodium-mercapto-2,Z-dicyanoethene remain in the form of white,hygroscopic crystals which do not melt until a temperature of 300C isreached. The corresponding l-amino-l-mercapto- 2,2-dicyanoethene,liberated by means of hydrochloric acid, melts at 170172C.

Analogously, the following mercaptides or mercaptans are obtained:

a. l-Methylamino-l-mercapto-2,Z-dicyano-ethene,

mp. C.

b. 1 -Dimethylaminol -mercapto-2,2-dicyanoethene, m.p. l57160C. c.1-Piperidino-1-mercapto-2,2-dicyano-ethene Analysis:

C H N S Calculated. 55.9 5.7 21.8 16.5 Found: 55.1 6.1 20.9 17.2

d. 1-Pyrrolidino-1-mercapto-2,Z-dicyano-ethene Analysis:

C 1-1 N S Calculated: 5 3.6 5.0 23 .4 17 .9 Found: 52.8 5.9 22.9 1.82

Calculated: 49.2 21.5 16.4

Found: 50.2 5.2 20.3 15.9

f. 1 -M eth ylamino- 1 -sodium-mercapto-2,Z-dicyanoethene, Analysis:

C H N Na Calculated: 37.1 2.5 25.1 14.3 Found: 36.7 2.9 24.5 15.1

EXAMPLE 2 Analogously to Example 1, 186.2 g. (1 mol) of 1- amino-l-methyl-mercapto-2-cyano-2-carbethoxyethene, is reacted with 169 g. of a33 percent solution of sodium hydrogen sulfide to obtainl-amino-l-sodium-mercapto-2-cyano-2-carbethoxy-ethene in the form ofwhite, hygroscopic crystals which do not melt until 310C. By treatmentwith sulfuric acid, l-amino- 1-mercapto-2-cyano-2-carbethoxy-ethene isobtained, m.p.155156C.

In place of the sodium hydrogen sulfide, it is possible to employ, withthe same success, potassium, ammonium, calcium or magnesium hydrogensulfide. The reaction can also be conducted with the correspondingsulfides.

Analogously, the following compounds are obtained:

a. 1-Methy1amino-1-sodium-mercapto-2-cyano-2- carbethoxy-ethene,Analysis:

C H N Na Calculated: 40.6 4.4 13.5 11.1 Found: 39.8 4.5 3.2 11.4

b. 1-Methylamino-l-mercapto-2-cyano-2-carbethoxy-ethene, m.p. 5 8C.

0. l-Dimethylamino-l-sodium-mercapto-2-cyano-2- carbethoxy-ethene,Analysis:

C H N Na Calculated: 43.2 4.9 12.6 10.4 Found: 41.8 4.6 12.9 9.7

d. 1-Dimethylamino-l-mercapto-2-cyano-2-carbethoxyethene, m .p. 5 354C.e. l-1sopropylamino-1-sodium-mercapto-2-cyano-2- carbom ethoxy-ethene,Analysis:

C H N Na Calculated: 43.2 4.9 12.6 10.4 Found: 41.8 4.6 12.9 9.7

f. 1-Dimethylamino-1-mercapto-2-cyano-2-methylaminocarbonyl-ethene, m.p.144-146C.

g. 1-Amino-1-mercapto-2-cyano-2-aminocarbonylethene, m.p. 162C(decomposition).

h. l-Dimethylamino-1-mercapto-2-cyano-2-aminocarbonyl-ethene, m.p. 147C(decomposition).

i. 1-Morpholino-1-mercapto-2-cyano-2-carbethoxyethene, m.p. 74-76C.

EXAM PLE 3 24.6 g. of sodium acetate (0.3 mol) is added to a solution of16.1 g. of 1-methy1amino-l-sodium-mercapto-2,2-dicyano-ethene (0.1 mol)in 400 ml of water; thereafter, a solution of 16.9 g. of silver nitratein 100 ml of water is added dropwise under stirring at room temperature.The stirring is continued for 1 hour, and the resultantl-methylamino-l-si1ver-mercapto-2,2-

EXAMPLE 4 5 g. l-amino-l-mercapto-2,2-dicyano-ethene is dissolved at Cin 200 ml of 25 percent ethanol and mixed, under agitation, with asolution of 4 g. of copper(I1)-acetate in 50 ml of water. Theyellow-green copper salt is at once separated and, after stirring for ahour and being cooled to room temperature, is vacuum-filtered and thenwashed first with water and thereafter with acetone. Yield: 4.7 g. 78.5percent of theory; m.p. above 310C.

Analysis: C H Cu Calculated: 30.85 1.3 204 Found: 30.20 1.6 20.6

correspondingly, the following copper salts are produced, all of whichhave a melting point of 310C or above.

1-dimethylamino-1-copper-mercapto-2,2-dicyanoethene1-n-propylamino-1-copper-mercapto-2-cyano-2- amino-carbonyl-ethenel-n-butylamino-l -copper-mercapto-2-cyano-2- carbo-methoxy-ethene 1-amino- 1 -copper-mercapto-2-cyano-2-aminocarbonyl-ethene.

EXAMPLE 5 Analogously to Example 4, with the use of zinc(1l)- acetateacetate instead of copper(11( )-acetate, the corresponding zinc salt of1-amino-1-mercapto-2,2- dicyano-ethene is obtained as a white,practically insoluble powder which does not melt until 310C.

Analysis:

C H Zn Calculated: 30.7 1.3 20.8 Found: 29.2 1.5 22.1

correspondingly, the following compounds are obtained:

1-amino-1-zinc-mercapto-2,Z-dicyano-ethene1-isopropylamino-1-zinc-mercapto-2,Z-dicyanoethene1-morpholino-l-zinc-mercapto-2,Z-dicyano-ethene1-dimethylamino-1-zinc-mercapto-2-cyano-2- methylaminocarbonyl-ethene 1-n-butylaminol -zinc-mercapto-2-cyano-2- aminocarbonyl-ethene.

EXAMPLE 6 A solution of 2.94 kg of 1-amino-l-sodiurn-mercapto-2,2-dicyano-ethene in 90 l. of water is mixed underagitation with 2.2 kg of concentrated hydrochloric acid and at 20C, 1.23l. of 30 percent hydrogen peroxide is admixed therewith during a periodof 5 minutes. The disulfide quickly begins to separate in the form offine, white crystals. The agitation is continued for another half hour;then the reaction mixture is vacuum-filtered and washed with a largeamount of water. After drying, 2.29 kg 92.4 percent of theory) of bis-(1-amino-2,2- dicyano-ethenyl)-disulfide is obtained, which productstarts, without previous melting, to decompose at 180C while assuming ared color.

Analogously, the following compounds are obtained:bis-(1-amino-2-cyano-2-carbethoxy-ethenyl)-disulfide, m.p. 18,4186C;bis-( l-methylamino-2-cyano-2-carbethoxy-ethenyl disulfide, m.p.166-168C; bis-(1-dimethylamino-2-cyano-2-carbethoxy-ethenyl)-disulfide,m.p. 136-138C; bis-( l-ethylamino-2,Z-dicyano-ethenyl)-disulfide,

m.p. 137-139C; bis-( 1 -methylamino -2 ,Z-dicyano-ethenyl)-disulfide,

decomposition from 130C, red coloring.

7 EXAMPLE 7 110 g. of 1-mercapto-l-dimethylamino-2-cyano-2-methylaminocarbonyl-ethene is suspended in 1,100 ml of acetonitrile "and55 ml of dimethyl formamide. Under agitation, chlorine is introducedinto the suspension at room temperature and at a rate such that thetemperature, after 5 minutes, is increased to 50C. From the presentlyclear solution, crystals separate during cooling, which crystals arevacuum-filtered and washed with a small amount of ice-cold acetonitrile.After drying, the desired bis-(1-dimethy1amino-2-cyano-2-methylaminocarbonylethenyl)-disulfide is obtained in the form ofyellow-white crystals having a melting point of 214215C.

EXAMPLE 8 A solution of 19.5 g. of Na S in 400 ml of methanol is addeddropwise at the boiling point in the course of 10 minutes to a solutionof 50.5 g. of 1-chloro-1- isopropylamino-2-cyano-2-carbomethoxy-ethene;m.p.

77C, in 400 ml of methanol. Then, the mixture is boiled under reflux for30 minutes. After cooling, the

separated NaCl is filtered off. Subsequently, thesolubornethoxy-2-cyano-ethenyl)-disulfide precipitates in crystallineform, m.p. l33134C.

In place of the l-chloroethene compounds, the corresponding l-bromoorl-iodo-compound can likewise be employed. However, since these compoundsare substantially more reactive, but also less stable, the reaction withsulfides or hydrogen sulfides is suitably conducted at lowertemperatures (between and compounds are 15 m.p. 205-207c.

g. Bis-(1-pyrrolidino-2,2-dicyano-ethenyl)-disulfide, v m.p. 187-189C.

h. Bis-(1-dimethylamino-2,Z-dicyano-ethenyl)-disul- 2 fide,decomposition from 260C.

II. PESTICIDAL COMPOSITIONS EXAMPLE A Sprayable Powder 50%1-Methylamino-1-mercapto-2,2-dicyanoethene 0.5% Alkyl naphthalenesulfonate 1% silicic acid 48.5% Bole EXAMPLEB Granulate 5%l-Morpholino-l-mercapto-2,2-dicyano-ethene copper or zinc salt 3%Gelatin 10% Bole 5% Wheat flour 77% Bran EXAMPLE c Sprayable Powder 75%Bis-(1-dimethylamino-2cyano-2-aminocarbonylethenyl)-disulfide 8% Oleicacid-N-methyl tauride 17% Chalk EXAMPLE D Sprayable Powder 80% 1-Amino-1 -zinc-mercapto-2-cyano-2-carbethoxyethene 5% Oleicacid-N-methyl tauride 15% Siliceous chalk The components are finelyground together. By dilution with water, a finely divided emulsion isobtained which can be sprayed or atomized.

EXAMPLE E 1 1 12 In place of the aforesaid disulfide, it is alsopossible with the provision that when R., is hydrogen, or Nl-lf', toemploy l-dimethylamino-l -mercapto-2,2-dicyano- R does not representCOOR ethene. 2. A compound as defined by claim 1 wherein R is Nl-lf.EXAMPLE F 5 3. A compound as defined by claim 1 wherein R is SprayablePowder 50%Bis-(l-methylamino-2-cyano-methylaminocarbonyl-ethenyl)-disulfide 0.5%Dialkyl naphthalene sulfate R1 0:0 Sulfite waste liquor powder 39.5%Bole f As the active ingredient, it is also possible to utilize bis-( 1-methylamino-2,2-dicyano-ethenyl)-disulfide.

EXAMPLE G 4. A compound as defined by claim 1 wherein said Granulate 8%1 Amino l copper mercaptoaldicyanoethene compound isl-ammo-l-mercapto-2,2-dicyano-ethene. 3% Gelatin 5. A compound asdefined by claim 1 wherein said 80% Bran compound isl-methylamino-1-mercapto-2,2-dicyano- 9% Bole 6. A compound as definedby claim 1 wherein said EXAMPLE [-1 compound is1-dimethylamino-l-mercapto-2,2- D fn A t dicyano-ethene.

us 1 en 2% Bisil-methylamino-2-cyano-l-carbethoxyethe- 7. A com-poupd asde-fined by-clalm l wherem :Sad compound isbis-(l-ammo-2,2-dicyano-ethenyl)-d|sulnyl)-disulfide and 98% Talc 8. Acompound as defined by claim 1 wherein said are ground together andthereafter distributed by dustcompound is bis (l methy|amino 2,2 dicyan0ethe mg.

. nyl)-disulfide. The preceding examples can be repeated with similar 9.A compound as defined by claim 1 wherein Said success by substitutingthe generically or specifically compound is bis (1 dimethy|amin 2,2dicyano ethe described reactants and/or operating conditions of this l)di lfid invention for those used in the preceding examples.

10. A compound as defined by claim 1 wherein said From the foregoingdescription, one skilled in the art compound is bis-(l-amino-2-cyano-2-carbethoxy-ethecan easily ascertain the essentialcharacteristics of this l) di lfid invention, and without departing fromthe spirit and 1 A-compound as d fi d by ciaim 1 wherein Said scopethereof, can make various changes and modificacompound is i 1 h i 2 2-tions of the invention to adapt it to various usages and b h h l di ]fldconditions- 12. A compound as defined by claim 1 wherein said Theembodiments of the invention in which an exclucompound i 1. -2- 2- siveproperty or privilege is claimed are defined as folb h th l)-di ulfidIOWSI 13. A compound as defined by claim 1, wherein R A Compound of theFormula and R each is alkyl of one to five carbon atoms.

14. A compound as defined by claim 1, wherein R NC gi and R each ishydrogen.

R2 15. A compound as defined by claim 3, wherein R and R each is alkylof one to five carbon atoms. I 16. A compound as defined by claim 3,wherein R s and R each is hydrogen.

17. A process for the preparation of a compound of the formula whereinR, is CN or 000R,, R and R each is hydrogen or alkyl of one to fivecarbon atoms, and R. N\ R is hydrogen, NHK, or R;

wherein s R represents CN; CONH CONHCH or COOR m R and R, eachrepresents hydrogen or alkyl of one to five carbon atoms, and R,represents hydrogen, NH}, or an equivalent of a 3 metal cation,

said process comprising reacting a starting material with an alkalimetal, an alkaline earth metal or amof the formula monium sulfide orhydrosulfide in an inert solvent at temperatures of between C and +100C.18. A process as defined by claim 17, wherein R is NC R5; 5 CN.

R 19. A process as defined by claim 18, wherein R and 1 R each is alkylof one to five carbon atoms. R1 20. A process as defined by claim 18,wherein R and a R each is hydrogen.

1O 21. A process as defined by claim 17 further comprising the step ofoxidizing said compound produced wherein therein to form thecorresponding disulfide.

R to R having the previously indicated meanings, Aprocess a5 defined yClaim 17 wherein aid and halogen lS Cl, Br or 1.

R represents halogen or lower alkylthio',

2. A compound as defined by claim 1 wherein R4 is NH4 .
 3. A compound asdefined by claim 1 wherein R4 is
 4. A compound as defined by claim 1wherein said compound is 1-amino-1-mercapto-2,2-dicyano-ethene.
 5. Acompound as defined by claim 1 wherein said compound is1-methylamino-1-mercapto-2,2-dicyano-ethene.
 6. A compound as defined byclaim 1 wherein said compound is1-dimethylamino-1-mercapto-2,2-dicyano-ethene.
 7. A compound as definedby claim 1 wherein said compound isbis-(1-amino-2,2-dicyano-ethenyl)-disulfide.
 8. A compound as defined byclaim 1 wherein said compound isbis-(1-methylamino-2,2-dicyano-ethenyl)-disulfide.
 9. A compound asdefined by claim 1 wherein said compound isbis-(1-dimethylamino-2,2-dicyano-ethenyl)-disulfide.
 10. A compound asdefined by claim 1 wherein said compound isbis-(1-amino-2-cyano-2-carbethoxy-ethenyl)-disulfide.
 11. A compound asdefined by claim 1 wherein said compound isbis-(1-methylamino-2-cyano-2-carbethoxy-ethenyl)-disulfide.
 12. Acompound as defined by claim 1 wherein said compound isbis-(1-dimethylamino-2-cyano-2-carbethoxy-ethenyl)-disulfide.
 13. Acompound as defined by claIm 1, wherein R2 and R3 each is alkyl of oneto five carbon atoms.
 14. A compound as defined by claim 1, wherein R2and R3 each is hydrogen.
 15. A compound as defined by claim 3, whereinR2 and R3 each is alkyl of one to five carbon atoms.
 16. A compound asdefined by claim 3, wherein R2 and R3 each is hydrogen.
 17. A processfor the preparation of a compound of the formula wherein R1 representsCN; CONH2; CONHCH3; or COOR2, R2 and R3 each represents hydrogen oralkyl of one to five carbon atoms, and R4 represents hydrogen, NH4 , oran equivalent of a metal cation, said process comprising reacting astarting material of the formula wherein R1 to R3 having the previouslyindicated meanings, and R5 represents halogen or lower alkylthio, withan alkali metal, an alkaline earth metal or ammonium sulfide orhydrosulfide in an inert solvent at temperatures of between -20*C and+100*C.
 18. A process as defined by claim 17, wherein R1 is CN.
 19. Aprocess as defined by claim 18, wherein R2 and R3 each is alkyl of oneto five carbon atoms.
 20. A process as defined by claim 18, wherein R2and R3 each is hydrogen.
 21. A process as defined by claim 17 furthercomprising the step of oxidizing said compound produced therein to formthe corresponding disulfide.
 22. A process as defined by claim 17wherein said halogen is Cl, Br or I.